Embodiment
Below specify the present invention.
Light diffusion plate for liquid crystal display of the present invention is a laminate structure, has styrene resin layer (B) at least one face of agent of low hygroscopicity resin bed (A).
The agent of low hygroscopicity resin that uses among the present invention is to be resin below 0.2% according to 24 hours the water-intake rate that JIS K7209 tries to achieve.To become the moisture absorption of the problem that exists in market warpage in order improving, to need water-intake rate to be at least below 0.2%.Preferred below 0.18%, more preferably below 0.15%, consider from practicality, preferred more than 0.03%.
Measure by this method, for example, the water-intake rate of so-called acrylic resin is 0.3%, and polycarbonate resin is 0.2%, and styrene resin is 0.1%.Can contain methyl methacrylate and styrene acrylic acid-styrene copolymer (so-called MS resinoid), and in 0.1%~0.3% scope according to its copolymerization ratio as the monomeric unit of copolymerization.The many more water-intake rates of methyl methacrylate are high more.The copolymerization ratio of methyl methacrylate units and styrene units is that 60: 40 o'clock water-intake rates are 0.22%, and the copolymerization ratio is that 80: 20 o'clock water-intake rates are 0.26%, and the copolymerization ratio is that 50: 50 o'clock water-intake rates are 0.2%.If the copolymerization ratio is 20: 80, styrene ratio when improving, water-intake rate is 0.14%.The water-intake rate of polyolefin resins such as polythylene resin, fluororesin is below 0.01%, the water-intake rate of PET resin is 0.6%.
Therefore, operable resin among the present invention can be enumerated polycarbonate resin, styrene resin, contain MS resinoid, polyolefin resin, fluororesin of 50% above styrene monomer etc.Wherein, preferably contain the above styrene monomer of 50 weight % styrene resin, contain the above styrene monomer of 50 weight % the MS class to fat or polycarbonate resin, more preferably polystyrene resin or polycarbonate resin.These resins also can mix use more than 2 kinds.Most preferably polystyrene accounts for 100% situation.
Styrene resin described in the present invention, be meant be essentially the independent polymkeric substance of styrene or contain have in above 1 molecule of 50 weight % 1 can free radical polymerization two keys styrene monomer and less than 50 weight % can with the copolymer resin of the unsaturated monomer of its copolymerization (below, with have in 1 molecule 1 can free radical polymerization the monomer of two keys be called monofunctional monomer, with have in 1 molecule at least 2 can free radical polymerization the monomer of two keys be called polyfunctional monomer).
For example, the polymkeric substance that can use the polymerization of phenylethylene monofunctional monomer to obtain; The multipolymer that phenylethylene monofunctional monomer and other monofunctional monomer polymerization are obtained; The cross-linked polymer that phenylethylene monofunctional monomer and polyfunctional monomer polymerization are obtained; Make cross-linked polymer that phenylethylene monofunctional monomer, other monofunctional monomer and polyfunctional monomer polymerization obtain etc.As the polymerization that is used to obtain these styrenic polymers, adopt suspension polymerization, microsuspension polymerization method, emulsion polymerization method, dispersion copolymerization method etc. usually.
As the phenylethylene monofunctional monomer in the styrene resin, except that styrene, can also enumerate halogenated styrenes such as chlorostyrene, bromstyrol, or ring-alkylated styrenes such as vinyltoluene, α-Jia Jibenyixi, p-methylstyrene, t-butyl styrene etc., also can use the two or more of them as required.
As the monofunctional monomer beyond the phenylethylene monofunctional monomer in the styrene resin, for example can enumerate: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid-2-Octyl Nitrite, methacrylic acid-methyl acrylic esters such as 2-hydroxy methacrylate; Esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2-ethyl caproite, 2-Hydroxy ethyl acrylate; Vinyl cyanide etc. can use the two or more of them as required.Wherein, methyl acrylic ester such as preferable methyl methyl acrylate.
As the polyfunctional monomer in the styrene resin, for example can enumerate: 1, the divalent of polyalcohols such as 4-butanediol dimethylacrylate, neopentylglycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethylacrylate, TEG dimethylacrylate, propylene glycol dimethylacrylate, four propylene glycol dimethylacrylates, trimethylol-propane trimethacrylate, pentaerythrite tetramethyl acrylate or surpass the methyl acrylic ester of divalent; 1, the divalent of polyalcohols such as 4-butanediol diacrylate, neopentylglycol diacrylate, glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, propylene glycol diacrylate, four propylene glycol diacrylates, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate or surpass the esters of acrylic acid of divalent; Aromatic series such as divinylbenzene, diallyl phthalate polyfunctional monomers etc. can use the two or more of them as required.
As the MS resinoid that contains 50% above styrene monomer, the heavy polymer that can use the polymerization of acrylic compounds monofunctional monomer to obtain for example; The heavy polymer that acrylic compounds monofunctional monomer and other monofunctional monomer polymerization are obtained; The cross-linked polymer that acrylic compounds monofunctional monomer and polyfunctional monomer polymerization are obtained; Make cross-linked polymer that acrylic compounds monofunctional monomer, other monofunctional monomer and polyfunctional monomer polymerization obtain etc.Obtain the resinoid polymerization of MS as being used to, adopt suspension polymerization, microsuspension polymerization method, emulsion polymerization method, dispersion copolymerization method etc. usually.
As above-mentioned acrylic compounds monofunctional monomer, for example can enumerate: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid-2-Octyl Nitrite, methacrylic acid-methyl acrylic esters such as 2-hydroxy methacrylate; Esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2-ethyl caproite, 2-Hydroxy ethyl acrylate; Methacrylic acid, acrylic acid etc. can use the two or more of them as required.
As the monofunctional monomer beyond the aforesaid propylene acids monofunctional monomer, can enumerate illustrative monomer of phenylethylene monofunctional monomer or vinyl cyanide etc. in the aforementioned styrenic polymer, can use the two or more of them as required.In addition, as the polyfunctional monomer in the acrylic polymers, can enumerate with aforementioned styrene resin in the same monomer of illustrative polyfunctional monomer, can use the two or more of them as required.
On one side, preferred two surfaces at least of above-mentioned hygroscopicity resin layer (A), lamination contains 50% above styrene resin and mixes the styrene resin layer (B) of 3.5~5 mass parts ultraviolet light absorbers with respect to these resin 100 mass parts.
Styrene resin as used herein, the copolymerization ratio that can enumerate aforementioned styrene monomer is the styrene resin more than 50%.Styrene resin can be and the identical resin of styrene resin that uses as hygroscopicity resin layer (A), also can use the different styrene resin of copolymerization ratio.Wherein, the copolymerization ratio of optimization styrene class monomer is the resin more than 80%, most preferably polystyrene.
As the resin except that styrene resin that contains, 24 hours the water-intake rate that consideration is tried to achieve according to JIS K7209 is the agent of low hygroscopicity resin below 0.2%, polycarbonate resin is arranged, contain MS resinoid, polyolefin resin, fluororesin of 50% above styrene monomer etc.
The resinoid content of optimization styrene is more than 80%, more preferably more than 90%, most preferably polystyrene accounts for 100% of resin.
In the light diffusing sheet of the present invention, in order to give light diffusion function, can be in above-mentioned agent of low hygroscopicity resin bed (A) the mixed light diffusant.In addition, also can the mixed light diffusant in the styrene resin layer (B).
The optical characteristics of light diffusing sheet according to the structure, the number of cold-cathode tube, the kind and the brightness specifications of blooming of the Staight downward type backlight of assembling, is designed to transmitance respectively and is 50~80%, the light diffusivity is 30~90%.In order to reach this scope, can suitably regulate the granula and the combined amount of light diffusing agent.
The preferred mean grain size of light diffusing agent of mixing is approximately 0.1~50 μ m, can mix 0.1~30 mass parts with respect to agent of low hygroscopicity resin 100 mass parts.It is concavo-convex when the purpose to give light diffusing sheet in order to the granularity that has with light diffusing agent as described later, the light diffusing agent that preferable particle size is big.
Light diffusing agent roughly is divided into two kinds of mineral-type and organic classes.
As the mineral-type light diffusing agent, for example can enumerate: lime carbonate, barium sulphate, titanium dioxide, aluminium hydroxide, silicon dioxide, glass, talcum, mica, white carbon, magnesium oxide, zinc paste etc.These light diffusing agents can carry out surface treatment with fatty acid etc.
As organic class light diffusing agent, for example can enumerate: styrenic polymer particle, acrylic polymers particle, type siloxane polymer particle etc.Can preferably use weight-average molecular weight be 500,000~5,000,000 heavy polymer particle or in acetone the gel fraction during dissolving be cross-linking polymer particle more than 10%.
As the styrenic polymer particle, can preferably use contain have in above 1 molecule of 50 weight % 1 can free radical polymerization two keys styrene monomer polymer particle (below, sometimes have in 1 molecule 1 can free radical polymerization the monomer of two keys call monofunctional monomer, have in 1 molecule at least 2 can free radical polymerization the monomer of two keys call polyfunctional monomer).For example, the heavy polymer particle that can use the polymerization of phenylethylene monofunctional monomer to obtain; The high molecular weight copolymer particle that phenylethylene monofunctional monomer and other monofunctional monomer polymerization are obtained; The cross-linking polymer particle that phenylethylene monofunctional monomer and polyfunctional monomer polymerization are obtained; Make cross-linking polymer particle that phenylethylene monofunctional monomer, other monofunctional monomer and polyfunctional monomer polymerization obtain etc.As the polymerization that is used to obtain these styrenic polymer particles, adopt suspension polymerization, microsuspension polymerization method, emulsion polymerization method, dispersion copolymerization method etc. usually.
As the phenylethylene monofunctional monomer in the styrenic polymer particle, except that styrene, can also enumerate halogenated styrenes such as chlorostyrene, bromstyrol, or ring-alkylated styrenes such as vinyltoluene, α-Jia Jibenyixi etc., also can use the two or more of them as required.
As the monofunctional monomer beyond the phenylethylene monofunctional monomer in the styrenic polymer particle, for example can enumerate: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid-2-Octyl Nitrite, methacrylic acid-methyl acrylic esters such as 2-hydroxy methacrylate; Esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2-ethyl caproite, 2-Hydroxy ethyl acrylate; Vinyl cyanide etc. can use the two or more of them as required.Wherein, methyl acrylic ester such as preferable methyl methyl acrylate.
As the polyfunctional monomer in the styrenic polymer particle, for example can enumerate: 1, the divalent of polyalcohols such as 4-butanediol dimethylacrylate, neopentylglycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethylacrylate, TEG dimethylacrylate, propylene glycol dimethylacrylate, four propylene glycol dimethylacrylates, trimethylol-propane trimethacrylate, pentaerythrite tetramethyl acrylate or surpass the methyl acrylic ester of divalent; 1, the divalent of polyalcohols such as 4-butanediol diacrylate, neopentylglycol diacrylate, glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, propylene glycol diacrylate, four propylene glycol diacrylates, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate or surpass the esters of acrylic acid of divalent; Aromatic series such as divinylbenzene, diallyl phthalate polyfunctional monomers etc. can use the two or more of them as required.
The refractive index of styrenic polymer particle is generally about 1.53~about 1.61 according to its constituent.Have generally that phenyl is many more, to have a halogeno-group in addition many more, then refractive index is tended to high more.
As the acrylic polymers particle, can preferably use and contain the polymer particle of the above acrylic compounds monofunctional monomer of 50 weight % as monomeric unit.For example, the polymer particle that can use the polymerization of acrylic compounds monofunctional monomer to obtain; The copolymer particle that acrylic compounds monofunctional monomer and other monofunctional monomer polymerization are obtained; The cross-linking polymer particle that acrylic compounds monofunctional monomer and polyfunctional monomer polymerization are obtained; Make cross-linking polymer particle that acrylic compounds monofunctional monomer, other monofunctional monomer and polyfunctional monomer polymerization obtain etc.As the polymerization that is used to obtain these acrylic polymers particles, adopt suspension polymerization, microsuspension polymerization method, emulsion polymerization method, dispersion copolymerization method etc. usually.
As the acrylic compounds monofunctional monomer in the acrylic polymers particle, for example can enumerate: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid-2-Octyl Nitrite, methacrylic acid-methyl acrylic esters such as 2-hydroxy methacrylate; Esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2-ethyl caproite, 2-Hydroxy ethyl acrylate; Methacrylic acid, acrylic acid etc. can use the two or more of them as required.
As the monofunctional monomer beyond the acrylic compounds monofunctional monomer in the acrylic polymers particle, can enumerate with aforementioned styrenic polymer particle in same monomer of phenylethylene monofunctional monomer and vinyl cyanide etc., can use the two or more of them as required.Wherein, optimization styrene.In addition, as the polyfunctional monomer in the acrylic polymers particle, can enumerate with aforementioned styrenic polymer particle in the same monomer of polyfunctional monomer, can use the two or more of them as required.
The refractive index of acrylic polymers particle is generally about 1.46~about 1.55 according to its constituent.It is also the same with the styrenic polymer particle, has generally that phenyl is many more, to have a halogeno-group in addition many more, and then refractive index is tended to high more.
As the type siloxane polymer particle, can preferably use the polymer particle that is commonly referred to as silicon rubber or be called as silicones and the following polymer particle of normal temperature as solid.The type siloxane polymkeric substance can preferably be made by the hydrolysis and the condensation of chlorosilane classes such as dimethyldichlorosilane, diphenyl dichlorosilane, phenylmethyldichloroislane, methyl trichlorosilane, phenyl trichlorosilane.The polymkeric substance that obtains like this can further pass through benzoyl peroxide, peroxidating-2,4-dichloro-benzoyl, chloro benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2, the effect of superoxide such as 5-two (t-butylperoxy) hexane and crosslinked, in addition, if terminal have a silanol base, then can with alkoxyl silicone alkanes condensation cross-linking.As this polymkeric substance, preferred per 1 silicon atom is in conjunction with the cross-linked polymer of 2~3 organic groups.
The type siloxane polymer particle can be by for example with broken the obtaining of type siloxane polymer machinery ground micro mist.In addition, when it is made, can as Japanese kokai publication sho 59-68333 communique be described, solidify under atomize by making curable polymer or its composition, thereby obtain spherical particle with linear organosiloxane block; Perhaps also can be as Japanese kokai publication sho 60-13813 communique be described, by in the aqueous solution of ammonia or amine with alkyltrialkoxysilaneand or its hydrolysis of partial hydrolysis condensation product and condensation, thereby obtain spherical particle.
The refractive index of type siloxane polymer particle is generally about 1.40~about 1.47 according to its constituent.It is many more generally to have on many more, the other silicon atoms of phenyl direct-connected organic group, and refractive index is tended to high more.
The light diffusing agent of these mineral-type or organic class can use separately, also can be used in combination of two or more according to the requirement of optical characteristics.
According to kind, particle diameter and the combined amount of light diffusing agent, definite substantially as the basic optical characteristic of light diffusing sheet, so-called transmitance or light diffusivity.
The thickness of slab of light diffusing sheet integral body depends on the structural design of LCD with Staight downward type backlight, be approximately 1mm~5mm, the laminate thickness of the styrene resin layer (B) of lamination is preferably 10 μ m~300 μ m and face integral body is that ± 50 μ m are with interior uniform laminate thickness.Laminate thickness is inhomogeneous more little, optical characteristics inhomogeneous also more little, and brightness irregularities on the liquid crystal display equipment screen or look inhomogeneous are also more little, and be therefore preferred.
Purpose as the scratch resistance that improves the light diffusing sheet surface of problem of the present invention, be reply because scuffing, the abrasive countermeasure that is caused with the inner anti-warpage pin contacts that is provided with of aforementioned Staight downward type backlight, with solve produce on the light diffusing sheet surface scar, this scar on liquid crystal display equipment screen as the visible problem of black scar.
In the past, when light diffusing sheet was made by acrylic resin, because the material resin of the anti-warpage pin of the surface ratio of acrylic resin is hard, so the light diffusing sheet surface can not produce scuffing, though the tip of anti-warpage pin is scratched cutting.
But, the problem that the moisture absorption warpage is arranged as previously mentioned, and after using MS resinoid or styrene resin, polycarbonate resin or olefine kind resin to replace acrylic resin as the light diffusing sheet material, because the skin hardness of these resins is obviously poor than acrylic resin skin hardness in the past, so the scuffing on light diffusing sheet surface becomes problem.
The light diffusing sheet surface preferably had small concavo-convex as previously mentioned in the past.
For example, in the patent documentation 7, disclose in order to make good hand touch, 10 mean roughness (representing with Rz) of the impression of preferred surface are 0.2~0.5 μ m, disclose in the patent documentation 8 in order to prevent dazzle, prevent dazzlingly that center line average surface roughness (representing with Ra) is preferably below the 0.25 μ m.Therefore, light diffusing sheet surface in the past preferably has small concavo-convex, and is no problem certainly on the quality.
Preferred small concavo-convex fully opposite on feature of the present invention and the light diffusing sheet in the past, its key be provided with on the light diffusing sheet surface big concavo-convex.Big concavo-convex by being provided with on the light diffusing sheet surface, diminish with the contact area of anti-warpage pin and contact resistance, frictional resistance diminish, sliding on the light diffusing sheet surface in the tip of anti-warpage pin, and is not easy to scratch.Surprisingly, the inventor finds, concavo-convex photostability also had remarkable result than big in the past like this.
Among the present invention, the expression of the arithmetic average roughness (representing with Ra) on the surface that defines in the concavo-convex method with JIS B0601 on light diffusing sheet surface need be 5~30 μ m.If arithmetic average roughness (Ra) that to be 5 μ m above is big concavo-convex, even then material is styrene resin or polycarbonate resin, also can prevent because of with the scratch surface that contacts of anti-warpage pin.In addition,, can prevent because the concavo-convex light loss that light scattering caused that causes, thereby can keep the high brightness of LCD by arithmetic average roughness (Ra) is set at below the 30 μ m.Be preferably 5 μ m~20 μ m, more preferably 7 μ m~18 μ m.
Need mix the ultraviolet light absorber of 3.5 mass parts~5 mass parts with respect to styrene resin 100 mass parts of styrene resin layer (B) in the light diffusing sheet of the present invention.Mix the above ultraviolet light absorber of 3 mass parts and can make the degraded appearance on light diffusing sheet surface, so generally do not consider.
But,, therefore have the few effect of oozing out of ultraviolet light absorber, and can significantly improve photostability, and can keep beautiful appearance because light diffusing sheet of the present invention surface has above-mentioned arithmetic average roughness.In order to prevent the xanthochromia of liquid crystal panel, the ultraviolet light absorber combined amount need be for more than 3.5 mass parts with respect to styrene resin 100 mass parts.On the other hand, if mix ultraviolet light absorber in a large number, then make the resin plasticizing of each layer, and degradation problem under decline of generation skin hardness or the brightness, therefore in order to keep the anti-scratch effect to greatest extent, satisfy the brightness specifications of LCD, need be for below 5 mass parts.Preferred 3.5 mass parts~4.5 mass parts, more preferably 3.5 mass parts~4 mass parts.
The kind of ultraviolet light absorber is not limited to benzophenone ultraviolet light absorber, benzotriazole ultraviolet light absorber, triazines ultraviolet light absorber, salicylate class ultraviolet light absorber, malonate class ultraviolet light absorber etc., and any commercially available ultraviolet light absorber can.These ultraviolet light absorbers can use separately also and can multiplely be used in combination.
In addition, also can mix this ultraviolet light absorber in the agent of low hygroscopicity resin bed (A).The combined amount of this moment is preferably set in order to keep tone below 1 mass parts.
Light diffusing sheet is configured as tabular by extrusion molding, injection moulding or compression molding usually.
The extrusion molding method is with the resin fusion and to be sheet material from the spinning head that is installed in the extruder front end be configured as tabular method with the mould ejection in extrusion shaper.From the molten resin of sheet material with the mould ejection, between a plurality of roll-type moulds, pass through usually, in cooling curing, form tabular that this roll-type die surface is transferred.Can freely control thickness of slab by the gap of regulating the roll-type mould.
Light diffusing sheet of the present invention is a laminated resin plate, the therefore preferred coetrusion that uses.That is, (A) layer is extruded by different extruders respectively with resin with (B) layer with resin, used interflow in the mould, also stacked at sheet material then.
Give on the light diffusing sheet surface concavo-convex, promptly give the method for the arithmetic average roughness of stipulating among the present invention, for example can be listed below method.(1) utilizes the particle diameter that above-mentioned light diffusing agent had that is blended in the resin, make the concavo-convex method of appearing in one's mind on the light diffusing sheet surface; (2) method of the concavo-convex and hot transfer printing of engraving on the mould that when making light diffusing sheet, uses; (3) transfer printing has been carried out the roll-type die surface of concavo-convex processing and the method for figuration in the extrusion molding process; (4) resemble direct scraping light diffusing sheet surface sandblast or the etching etc. and carve concavo-convex various technology such as method, any method can.
The light diffusing agent that mixes in the method as above-mentioned (1) can use the light diffusing agent of aforesaid mineral-type, organic class.The particle diameter of the light diffusing agent that mixes is preferably set to 10~50 μ m in order also to give concavo-convex.Usually, styrene resin and polycarbonate resin shrink when cooling, so the size of particle diameter is different with the surfaceness on surface.Roughness is roughly about half of particle diameter of light diffusing agent of mixing.
Combined amount is preferably 1~30 mass parts with respect to resin 100 mass parts of mixing.Preferably more than 1 mass parts, unusual and be preferably below 30 mass parts in order to provide uniformly concavo-convex on the light diffusing sheet surface for outward appearance that aggegation causes does not take place.
On the other hand, the engraving on mould of above-mentioned (2) is concavo-convex and with the method for its transfer printing, and operation provides big concavo-convex method on the light diffusing sheet surface be the easiest and only technology.Shrink because resin produced in when cooling, therefore at concavo-convex than about the concavo-convex big twenty percent of wishing to get of engraving on the die surface, and heat is transferred to the light diffusing sheet surface.
In addition, also there is the roll-type die surface that when extrusion molding, uses of above-mentioned (3) that concavo-convex method is provided.
The roll-type die surface is typically polished to mirror-like, and minute surface is transferred to the resin plate surface.Among the present invention, by at big concavo-convex of this roll-type mould surface engraving, can be to the surface of the light diffusing sheet that contacts with roller with concavo-convex transfer printing excipient.On this roll-type die surface the big concavo-convex method of engraving have several, can be by various processing method settings such as etching or electric field processing, electrodischarge machining, electron beam processing, plasma process, I.B.M., sandblasts.
As previously mentioned, because the resin cooling time shrinks, so transfer printing excipient concavo-convex concavo-convex less than what carve on the roll-type die surface easily to the light diffusing sheet surface.Therefore, can carve than the shape about the big twenty percent of target surface concaveconvex shape.
Light diffusing sheet can certainly be made by injection moulding or compression molding.At this moment, still engraving on the surface of shaping dies than target concavo-convex about concavo-convex big twenty percent, thus can be similarly with the concavo-convex transfer printing excipient of target to the light diffusing sheet surface.
If have concavo-convex that arithmetic average roughness of the present invention represents among the present invention on its surface of light diffusing sheet, then mix other functional additive and can further realize multifunction.If provide of the present invention concavo-convex from the teeth outwards, even it is also no problem then to have a plurality of functional layers of various functional layer.For example, light stabilizer, the agent of selection wavelength absorption, colorant, fire retardant, lubricant, antistatic agent etc., it can mix 0.001 weight %~5 weight % separately, also can laminate layers thickness is antistatic backing, electromagnetic wave shielding, gas barrier layer, photocatalyst layer, water repellent layer, cementation zone, anti-fog layer, stain-proofing layer, luminescent layer, diffusion layer, hyaline layer of 0.1 μ m~100 μ m etc.
What Fig. 1 represented is an example of the structure the when light diffusing sheet that the present invention obtains is used for the liquid crystal display television by using LCD.Cold-cathode tube 4 is arranged on the reflectance coating 5 in the framework 7 that is contained in liquid crystal panel 1 the inside, light diffusion layer 3 of the present invention is set between liquid crystal panel 1 and cold-cathode tube 4, is used to improve the blooming 2 of brightness.In addition, reflectance coating 5 is fixed on the light diffusing sheet 3 by anti-warpage pin 6.
Embodiment
Based on embodiment the present invention is described.
The light diffusing sheet of estimating in embodiment, the comparative example is as described belowly made by the laminated resin plate that utilizes coextrusion to be shaped to obtain 2 layers of formation.
2 of the single screw extrusion machines of extruder use screw diameter 100mm (agent of low hygroscopicity resin bed (A) is used) and 60mm (styrene resin layer (B) is used).With the resin melt kneading shown in table 1 and the table 2, and introduce the sheet material mould of width 1000mm with each extruder, will (A) layer with resin with (B) layer with after resin laminated, spray from spinning head.Then, by 3 ロ one Le of longitudinal type three-roller (Longitudinal type of width 1500mm, diameter 300mm), the light diffusing sheet of making thickness of slab 2mm, width 1000mm, length 1000mm.In addition, the thickness of styrene resin layer (B) is controlled to be thickness 50 μ m by the extrusion capacity of controlling 2 extruders, and total thickness of slab is controlled to be 2mm by the gap of regulating three-roller.
The whole surface of above-mentioned longitudinal type three-roller is carried out electrodischarge machining and is obtained the concavo-convex of size shown in the engraving behind the arithmetic average roughness shown in table 1 and the table 2 (Ra), and concavo-convex heat is transferred to and carries out excipient on the light diffusing sheet surface during by the roller gap.In addition, the evaluation method of the light diffusing sheet that obtains in each embodiment and the comparative example is as described below.
(1) surface average roughness: use surfaceness meter (Tokyo accurate system SURFCOM575A), the arithmetic average roughness of determination object thing (Ra) according to the method for JIS B0601 regulation.Cutoff with this moment is that 2.5mm, evaluation length are that 20mm measures.
(2) moisture absorption warpage: with the suction 98 hours under 60 ℃, the environment of 95%RH of the light diffusing sheet made, the light diffusing sheet that will be in saturated substantially suction state is installed to commercially available 32 inches having in the full run-down type cold-cathode tube LCD TV backlight, lights placement backlight 24 hours.
Because backlight illumination light diffusing sheet surface begins dehydration, drying, if the light diffusing sheet warpage then because light diffusing sheet touches liquid crystal panel, and makes the contact vestige appear as white wrinkle or wavy.Evaluation is judged by having or not this contact vestige of generation on the picture.If do not contact vestige then be evaluated as zero, and the light diffusing sheet that produces the contact vestige is evaluated as *.
(3) scratch resistance (anti-warpage pin friction): on the surface of the light diffusing sheet of making, put from (2) anti-warpage pin (the flame-retardant polystyrene olefine resin system of taking out in the Staight downward type backlight of identical commercially available LCD TV of use, most advanced and sophisticated R=1mm), reciprocating friction is 20 times under the state of the load that applies 1000g.
Afterwards, range estimation light diffusing sheet surface does not have scratch or abrades then that scratch resistance is evaluated as zero fully, be evaluated as if range estimation can be confirmed scar *.
(4) photostability: on the light diffusing sheet of making, use the distance irradiation 100J/cm of ultraviolet lamp (SEIMYUNG VACTRON corporate system SMDT51H) from 150mm
2Ultraviolet ray.By strong ultraviolet ray irradiation, light diffusing sheet surface deterioration xanthochromia.The yellow chromaticity of this light diffusing sheet is measured in use according to the color analyzer (TC1800 that Tokyo electricity look company makes) of JIS K7105.
The yellow chromaticity that calculates the light diffusing sheet behind the ultraviolet pre-irradiation changes as the xanthochromia degree.If the xanthochromia degree is 3 with the next ◎ that is evaluated as, the xanthochromia degree is to be evaluated as zero at 3~6 o'clock, and the xanthochromia degree is to be evaluated as △ at 6~9 o'clock, the xanthochromia degree be 10 be evaluated as when above *.In addition, the specification that requires of LCD TV is that the xanthochromia degree of being obtained in 60000 hours by the market wear life of LCD TV must be below 6.
(5) outward appearance: the surface of the light diffusing sheet that range estimation confirm to be made, the surface is evaluated as zero when no problem, attractive in appearance, observe that look inhomogeneous, stain, attachment, powder (powder blows), ooze out, outward appearances such as variable color, distortion all are evaluated as when unusual *.
(6) brightness: with the light diffusing sheet of making be installed in (2) in identical commercially available 32 inches LCD TV of use, light backlight.LCD screen shields full screen display by control device of the tv in vain.Afterwards, use nitometer (ト プ コ Application system BM-7) from brightness from the range determination center Screen of screen 500mm.
500cd~519cd is evaluated as zero, is evaluated as ◎ more than the 520cd, and it is qualified to represent; With 480cd~499cd be evaluated as △, less than 480cd be evaluated as *, represent defective.
Under the situation for commercially available LCD TV, the specification of requirement is that center Screen brightness is 500cd/cm
2More than.
The resin kind of using in embodiment, the comparative example is as described below.
PS: polystyrene resin (the system G9504 of Ps Japan Corp.), water-intake rate 0.1%
PC: polycarbonate resin (rising sun beautifies into corporate system PC-110), water-intake rate 0.2%
PMMA: acryl resin (the corporate system LP-1 of Asahi Chemical Industry), water-intake rate 0.3%
The MMAS:MS resin (MMA: St=60: 40, the system MS600 of chemical company of Nippon Steel), water-intake rate 0.22%
SMMA:MS resin 8MMA: St=20: 80, the system MS200 of chemical company of Nippon Steel, water-intake rate 0.14%.
[embodiment 1]
It at water-intake rate polystyrene resin (PS Japan Corp.'s system of 0.1%, trade name G9504) mixes type siloxane polymer particle (GE silicone Co., Ltd. of Toshiba system in 100 mass parts as organic class light diffusing agent, trade name ト ス パ one Le 120, mean grain size 2 μ m) 2 mass parts, and drop into agent of low hygroscopicity resin bed (A) with in the extruder.On the other hand, polystyrene resin (PS Japan Corp.'s system at water-intake rate 0.1%, trade name G9504) mixes ultraviolet light absorber (benzotriazole ultraviolet light absorber) 3.5 mass parts and in 100 mass parts as talcum (the Japanese talcum corporate system of mineral-type light diffusing agent, mean grain size 15 μ m) 5 mass parts, and drop into styrene resin layer (B) with in the extruder, carry out fusion and kneading.Afterwards, utilize coextrusion to form, make the light diffusing sheet of styrene resin layer (B) 50 μ, total thickness of slab 2mm by above-mentioned method.At this moment, for the longitudinal type three-roller, whole face is carved with the concavo-convex of arithmetic average roughness (Ra) 10 μ m, makes this concavo-convex roller surface configuration heat be transferred to the light diffusing sheet surface, forms big arithmetic average roughness on the light diffusing sheet surface thus.
Utilize the surfaceness meter that the arithmetic average roughness on this light diffusing sheet surface of making is measured, the result is: arithmetic average roughness (Ra) is concavo-convex slightly littler than what carve on the roller, is 8 μ m.
For the light diffusing sheet of such making, estimate moisture absorption warpage, scratch resistance, photostability, outward appearance, brightness projects by aforesaid method.Its result is as shown in table 1.Its no moisture absorption warpage as can be known, scratch resistance, photostability, outward appearance and brightness are all good, are the light diffusing sheets that meets target.
[embodiment 2~5]
Change the amount of the ultraviolet absorber that mixes in the styrene resin layer (B), the arithmetic average roughness size that to carve on the roll-type mould is changed into respectively: embodiment 2 is that 6 μ m, embodiment 4 are that 20 μ m, embodiment 5 are 30 μ m, in addition, make light diffusing sheet similarly to Example 1, carry out the evaluation of projects.Its evaluation result is as shown in table 1.As can be known from the results of Table 1, every specification that all meets the demands.
[comparative example 1~8]
Change the amount of the ultraviolet absorber that mixes in the styrene resin layer (B), the arithmetic average roughness that to carve on the roll-type mould is changed into respectively: comparative example 6 is that 6 μ m, comparative example 8 are 60 μ m for 4m, comparative example 7, in addition, make light diffusing sheet similarly to Example 1, carry out the evaluation of projects.Its evaluation result is as shown in table 1.
In addition, comparative example 5 and 6 surface average roughness are 0.2 μ m, but the roller that use this moment is that surperficial arithmetic average roughness (Ra) is the mirror roller roughly of 0.05 μ m.The mineral-type light diffusing agent that mixes appears in one's mind on the surface as the internal delustring agent, and the arithmetic average roughness on light diffusing sheet surface (Ra) is 0.2 μ m thus.
From the result of table 1 as can be seen, the specification that requires of each light diffusing sheet and LCD TV can not all satisfy.
If the minimizing ultraviolet light absorber, then brightness uprises, and can not satisfy photostability.If the amount of ultraviolet light absorber increases, then the plasticization effect owing to ultraviolet light absorber descends scratch resistant performance, also causes bad order, brightness to descend because look inhomogeneous, is not the light diffusing sheet that can satisfy the specification that requires.
On the other hand, if the arithmetic average roughness on light diffusing sheet surface is very little, then brightness is good, but scratch resistance descends.In addition, photostability is improved also satisfied.Otherwise if the arithmetic average roughness on surface further increases, then go up because the diffuse reflection of light causes light loss on the surface, increases and brightness is descended.
[embodiment 6~11, comparative example 9~38]
With the kind of the resin of use in agent of low hygroscopicity resin bed (A) or the styrene resin layer (B), the amount of the middle ultraviolet light absorber that mixes of styrene resin layer (B), the as shown in table 2 change of arithmetic average roughness on surface, make light diffusing sheet by method similarly to Example 1 in addition, carry out the evaluation of projects.Its evaluation result is as shown in table 2.